N-bromobutanimide → tert-butyl(2S,3S)-7-bromo-2-methyl-4-oxo-2,3,4,5-tetrahydro-1H-benzo[b][1,4]diazepin-3-ylcarbamate

HRID 1486074Notes

Reaction equation

HRID 1486074 reaction equation
[CH3:1][C@@H:2]1[NH:8][C:7]2[CH:9]=[CH:10][CH:11]=[CH:12][C:6]=2[NH:5][C:4](=[O:13])[C@H:3]1[NH:14][C:15](=[O:21])[O:16][C:17]([CH3:20])([CH3:19])[CH3:18].[Br:22]N1C(=O)CCC1=O>CN(C=O)C.[NH4+].[Cl-]>[Br:22][C:11]1[CH:10]=[CH:9][C:7]2[NH:8][C@@H:2]([CH3:1])[C@H:3]([NH:14][C:15](=[O:21])[O:16][C:17]([CH3:20])([CH3:19])[CH3:18])[C:4](=[O:13])[NH:5][C:6]=2[CH:12]=1

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 90082343tert-butyl(2S,3S)-2-methyl-4-oxo-2,3,4,5-tetrahydro-1H-benzo[b][1,4]diazepin-3-ylcarbamate

Product 1

HCID 131736773tert-butyl(2S,3S)-7-bromo-2-methyl-4-oxo-2,3,4,5-tetrahydro-1H-benzo[b][1,4]diazepin-3-ylcarbamateYield 96%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
0 °C

Procedure

To a 0° C. solution of tert-butyl(2S,3S)-2-methyl-4-oxo-2,3,4,5-tetrahydro-1H-benzo[b][1,4]diazepin-3-ylcarbamate (107.0 mg, 367 μmol) in DMF (2.45 ml) was added a solution of N-bromosuccinimide (68.6 mg, 386 μmol) in DMF (1.22 ml), dropwise over 5 min. The reaction was stirred at 0° C. for 30 min, then diluted with sat. aq. NH4Cl and extracted with EtOAc. The combined organic layers were washed with H2O, sat. aq. NaHCO3, and sat. aq. NaCl, dried over Na2SO4, and concentrated. The crude material was purified by flash chromatography to provide tert-butyl(2S,3S)-7-bromo-2-methyl-4-oxo-2,3,4,5-tetrahydro-1H-benzo[b][1,4]diazepin-3-ylcarbamate (130 mg, 96%) as a white solid. MS m/z 392/394 (MNa)+.

Workup

  1. extractionextracted with EtOAc
  2. washThe combined organic layers were washed with H2O, sat. aq. NaHCO3, and sat. aq. NaCl
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated
  5. customThe crude material was purified by flash chromatography

Sources & evidence

ORD record
ord-77439bf4ad4b4635977de8b62a853574
Source dataset
uspto-grants-2016_08
Patent number
US09422331B2

Reaction notes

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